Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/38—Coating with copper
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/208—Multistep pretreatment with use of metal first
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/285—Sensitising or activating with tin based compound or composition
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Definitions

• the present invention relates to accelerator solution additives and accelerator solutions for electroless metal plating.
• the present invention relates to an electroless copper plating method that employs such accelerator solution, and a composite material manufactured by such method.
• the pretreatment process for electroless copper plating consists of processes that include a conditioning process, etching process, acid wash process, palladium tin catalyst attachment process and an accelerator treatment process.
• a conditioning process etching process
• acid wash process palladium tin catalyst attachment process
• an accelerator treatment process e.g., an accelerator treatment process.
• palladium-tin colloid is adsorbed on a substrate surface, and by washing this material with water, the affixed colloid is hydrolyzed, and part of the tin forms a Sn(OH)Cl deposit.
• the rest of the tin is present as tetravalent tin, and the palladium is present as a palladium salt.
• treatment of the substrate is carried out using an acid such as hydrochloric acid, sulfuric acid or fluoroboric acid as accelerator, thereby causing dissolution of the tin salt that had formed the deposit.
• metallic palladium is produced by means of an acid reduction reaction with the palladium salt that had previously been removed from its colloidal state. The metallic palladium on the substrate thus functions as activated catalyst nuclei for metallic copper deposition during electroless copper plating.
• the present invention was developed in light of this state of affairs, and has the objective of offering additive containing accelerator solution suspension-inhibiting compounds having certain structures, which control the turbidity of accelerator solutions used in the above described activation processes.
• An additional objective is to offer an accelerator solution containing the aforementioned accelerator solution suspension-inhibiting compounds, which controls the turbidity when used.
• the present invention offers an electroless copper plating method that employs an accelerator solution containing the aforementioned accelerator solution suspension-inhibiting compounds.
• the invention also offers a composite material having a copper thin film produced by such method.
• the present invention provides additives for accelerator solutions, such solutions comprising one or more accelerator solution suspension-inhibiting compounds having certain structures.
• the present invention offers an electroless copper plating method that employs an accelerator solution containing one or more of the aforementioned accelerator solution suspension-inhibiting compounds and a composite material produced by said method.
• accelerator solution suspension-inhibiting compounds of the present invention include, but are not limited to, cysteine, cystine, thiomalic acid, methionine, thiodisuccinic acid, oxalic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, itaconic acid, 2-pyrrolidone-5-carboxylic acid, ascorbic acid, hydroquinone, aminopyrazine, 3-amino-1H-1,2,4-triazole, thiourea, urea, adenine, guanidine, allantoin, 2-amino-5-methyl-1,3,4-thiadiazole, hydroxylamine, cystamine, hydrazine, 1-(2,3-dihydroxypropyl)benzotriazole, 2-imidazolidinone, o-toluidine-4-sulfonic acid, 1,3-phenylenediamine-4-sulfonic acid, sulfosalicylic acid, phenols
• accelerator solution suspension-inhibiting compounds are cysteine, cystine, thiomalic acid, methionine, thiodisuccinic acid, oxalic acid, hydroxyacetic acid, glyoxylic acid, lactic acid, itaconic acid, 2-pyrrolidone-5-carboxylic acid, ascorbic acid, hydroquinone, aminopyrazine, 3-amino-1H-1,2,4-triazole, thiourea, urea, adenine, hydroxyethylidene diphosphonic acid and salts of these compounds.
• such compounds are cysteine, cystine, thiomalic acid, methionine, thiodisuccinic acid, ascorbic acid and slats of these compounds, still more preferably cysteine, cystine, thiomalic acid and salts of these compounds, and most preferably thiomalic acid and salts thereof.
• the salts of the accelerator solution suspension-inhibiting compounds presented above may be any salt that is water soluble and can be formed by the respective compounds.
• the compound has carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, phosphonic acid groups and/or boric acid groups, any substance that does not impede the objectives of the present invention can be used as the substances for forming salts with these groups are.
• Examples of salts that are formed include, but are not restricted to, alkali metal salts, alkaline earth metal salts and ammonium salts.
• these amines can form quaternary ammonium structures, and configurations may also be used that involve salts formed from said ammonium structures and acid.
• hydrazine configurations may be used that involve salts formed from hydrazinium compound and acid.
• acids that form salts include any acid that does not impede the objectives of the present invention, examples of which include, but are not limited to, hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid.
• water soluble used herein applies to any compound that has a degree of water solubility that allows dissolution in the accelerator solution.
• the accelerator solution additive pertaining to the present invention comprises one or more of the aforementioned accelerator solution suspension-inhibiting compounds.
• An increase in turbidity of the accelerator solution can be reduced or eliminated by the addition of the additive to the accelerator solution.
• the increase in accelerator solution turbidity is thought to occur when the tin released from the substrate upon immersion of the substrate with affixed palladium tin catalyst in the accelerator solution is converted into a compound that is insoluble in the accelerator solution, thus forming a sediment and increasing the turbidity of the accelerator solution.
• the mechanism whereby the increase in turbidity of the accelerator solution is controlled by the aforementioned accelerator solution suspension-inhibiting compound of the present invention is thought to involve the formation of a chelate between the accelerator solution suspension-inhibiting compound and tin ions in the accelerator solution, thereby preventing conversion of the tin into an insoluble compound.
• the accelerator solution additives of the present invention can also optionally contain acid other than the aforementioned accelerator solution suspension-inhibiting compound.
• the acid can be any acid, provided that it is an acid other than the accelerator solution suspension-inhibiting compound. Suitable examples include, but are not restricted to, hydrochloric acid, sulfuric acid, fluoroboric acid and alkylsulfonic acid. In addition, mixtures of two or more of the acids can be contained therein.
• the other acid is any acid that is commonly used in other accelerator treatment processes. It is preferable for the acid other than the accelerator solution suspension-inhibiting compound to be an alkylsulfonic acid, with methanesulfonic acid being particularly desirable.
• the ratio of the amount of the accelerator solution suspension-inhibiting compound to such other acid can be easily determined.
• the amount of accelerator solution suspension-inhibiting compound is an amount that allows the accelerator solution suspension-inhibiting compound to manifest superior prevention effects. It is also preferable for the amount of the other acid to be the amount that is required for the accelerator treatment.
• the present additive for accelerator solutions can also contain one or more nonionic surfactants.
• the nonionic surfactant can be of any type, provided that it does not interfere with the objectives of the present invention.
• nonionic surfactants include, but are not limited to, polyethylene glycol, polyoxyethylene alkylphenol, polyoxyethylene styrenated phenol, polyoxypropylene-polyoxyethylene polymer and glycerin.
• the present additives for accelerator solutions comprise accelerator solution suspension-inhibiting compound and one or more other acids and/or nonionic surfactant, then the additive can be constituted by these components alone, or can further comprise an appropriate solvent such as water.
• the accelerator solution of the present invention is preferably an aqueous solution that contains one or more accelerator solution suspension-inhibiting compounds and one or more other acids.
• the amount of accelerator solution suspension-inhibiting compound contained in the present accelerator solution is determined appropriately based on the conditions of use of the accelerator solution, and the type of accelerator solution suspension-inhibiting compound used therein. However, the amount is generally in the range of 0.001-50 g/L, with 0.005-10 g/L being preferred.
• the amount of the other acid is an amount that is commonly used in accelerator treatment processes, and is generally 25-100 g/L, with 40-60 g/L being preferred.
• the accelerator solution of the present invention can contain nonionic surfactant.
• the amount of nonionic surfactant is generally 0.001-20 g/L, with 0.01-15 g/L being preferred.
• the accelerator solution of the present invention can be used in any electroless copper plating method, provided that the method has an acceleration process whereby a palladium tin catalyst is activated.
• the accelerator solution of the present invention is used in electroless copper plating methods for accelerator treatment processes in which palladium tin catalyst is activated, it is possible to control any increase in turbidity that accompanies the use of such accelerator solutions.
• the present accelerator treatment process is carried out by contacting a substrate having palladium tin catalyst at its surface with the present accelerator solution. Any method can be used in order to bring about such contact between the substrate and the accelerator solution. For example, a method can be used wherein the substrate is immersed in the accelerator solution, or a method can be used wherein the accelerator solution is sprayed on the substrate.
• the bath temperature and treatment time can be set appropriately based on known conventional parameters.
• the palladium tin catalyst used in such electroless copper plating method can be any palladium tin catalyst.
• the catalyst that is used typically has the form of a catalyst liquid in which the palladium tin catalyst is present as colloid in a medium.
• Substrates that can be used in the present method can be composed of any resin, provided that the substrate has physical properties suitable to the objective for which it is used, such as strength and corrosion resistance. Substrates of any shape may be used without particular restrictions. It is preferable for the substrate to be a resin substrate, and resin substrates are not restricted to resin moldings, as they may also be composite materials formed by the interposition of a resin reinforcing material such as glass fiber reinforcing between resin layers. Alternatively, substrates can be used that are produced by the formation of a thin film of resin on a substrate composed of ceramic, glass, metal or various other members. The resin substrate can be composed of a single resin, or can be composed of multiple resins. In addition, a composite material can be formed by the application or lamination of resin on another substrate.
• palladium tin catalyst is first affixed to the substrate.
• Any method can be used as the method for affixing catalyst, provided that the method fixes the catalyst on the substrate.
• methods that may be cited involve the immersion of a substrate in the catalyst liquid or spraying of catalyst liquid on the substrate, but examples are not restricted to these.
• the substrate can be subjected, for example, to an immersion or spraying treatment in a commonly used conditioner as necessary prior to affixing the catalyst.
• a conditioning treatment, etching treatment or other such treatment can be carried out in order to facilitate affixing of the palladium or palladium tin catalyst on the substrate.
• metallic palladium is produced on the substrate by means of the accelerator treatment, and such metallic palladium functions as active catalyst nuclei for deposition of metallic copper during electroless copper plating.
• a copper thin film is directly formed on the resin substrate, thus producing a copper-resin composite material. While not intending to be bound by theory, it is thought that roughening of the deposited copper layer following the electroless copper plating treatment is prevented by the use of the present accelerator solution, because an increase in turbidity of the accelerator solution is prevented. As discussed above, this increase in turbidity of the accelerator solution is thought to be one of the causes of roughening.
• the aforementioned electroless copper plating method can be a copper sulfate plating method, copper cyanide plating method, copper pyrophosphate plating method or any well-known electrolytic copper plating method, but copper sulfate plating is preferred.
• Methanesulfonic acid and a nonionic surfactant were dissolved in purified water at concentrations of 48 g/L and 7.35 g/L respectively, thus producing an accelerator solution.
• Palladium tin catalyst suspension (0.15 g/L elemental palladium, 3.9 g/L elemental tin) was added to 200 mL of the accelerator solution so that the volume ratio was 0% (not added), 0.5% (final accelerator solution palladium concentration: 0.75 mg/L, tin concentration: 19.5 mg/L), 1.0% (final accelerator solution palladium concentration: 1.5 mg/L, tin concentration: 39 mg/L), 1.5% (final accelerator solution palladium concentration: 2.25 mg/L, tin concentration: 58.5 mg mg/L) or 5.0% (final accelerator solution palladium concentration: 7.5 mg/L, tin concentration: 195 mg/L), and the solution was stirred for 1 hr.
• the accelerator solution suspension inhibiting compounds shown in Table 1 were added at the concentrations indicated in Table 1 to an accelerator solution having the composition shown in Comparative Example 1, to produce the accelerator solutions of this Example.
• the turbidity of the accelerator solutions was measured by the same method as in Comparative Example 1.
• the accelerator solution suspension inhibiting compounds of the present invention inhibit turbidity increase in accelerator solutions caused by palladium tin catalyst.
• the concentrations of thiomalic acid, cysteine, cystine, hydroxyethylidene diphosphonic acid and thiodisuccinic acid were varied, and inhibitory effects on turbidity increase in accelerator solutions were investigated. Testing was carried out in the same manner as in Example 1 above, with the exception that the concentrations of the respective compounds, the palladium tin catalyst concentration and the stirring time were varied. The stirring time was 1 hr. for catalyst concentrations of 0-1.5%, and the stirring time was 1 hr., followed by 18 hr. of rest, for catalyst concentrations of 5% or greater.
• the copper foil of a copper-clad laminate board was etched away to produce a substrate (epoxy resin substrate FR-4; manufactured by Hitachi Kasei Kogyo; MCL-E-67), which was then cut to a square of 5 cm. After drying, the size of the substrate was measured. After size measurement, the substrate was treated for 5 min in a cleaner/conditioner, and was then warmed for 1 min, followed by rinsing with water for 1 min. The material was then treated for 1 min with 10% sulfuric acid, and was rinsed with water for 2 min.
• a substrate epoxy resin substrate FR-4; manufactured by Hitachi Kasei Kogyo; MCL-E-67
• the substrate was then treated for 1.5 min with pre-dip liquid, and was then immersed for 5.5 min in a palladium tin catalyst solution containing 0.15 g/L of palladium and 3.9 g/L of tin.
• the substrate was rinsed with water for 2 min, and the substrate was then immersed in a 30°C accelerator solution.
• the substrate was removed after 5.5 or 8 min, and the amount of elemental palladium and tin present on said substrate was measured with a high-frequency induction-coupled plasma analyzer.
• the accelerator solution was produced by dissolving methanesulfonic acid at a concentration of 48 g/L, and nonionic surfactant at a concentration of 7.35 g/L, in purified water.
• the method for measuring the amount of palladium or tin adsorbed on the substrate was carried out as described below. About 8 mL of aqua regia was added to substrate that had been treated as described above, and the solution was heated. After boiling, the resulting substrate solution was transferred into a graduated flask, and was adjusted to 100 mL using purified water. The substrate solution was then analyzed with a high-frequency induction-coupled plasma analyzer, and the palladium and tin amounts were quantified. The amount of tin or palladium adsorbed on the substrate was expressed as the amount of palladium or tin per unit surface area of substrate ( ⁇ g/cm 2 ).
• Accelerator solutions and substrate having adsorbed palladium tin catalyst were prepared using the same method as in Comparative Example 3, with the exception that thiomalic acid, cysteine, phosphoric acid, hydroxyacetic acid, hydroquinone, ascorbic acid or aminopyrazine at the concentration indicated in Table 3 was added to the accelerator solution of Comparative Example 3. The amount of palladium or tin present on the substrate after the accelerator treatment was measured using the same method.
• Comparative Example 3 and Example 3 are shown in Table 3.
• the residual ratio is a value that expresses the percentage of the amount of palladium or tin after treatment, taking the amount of palladium or tin prior to the accelerator treatment as 100%.
• the reason that the amounts of palladium and tin are different before treatment is that the amounts were evaluated using separate experiments.
• the adsorption amount of palladium and tin on substrate after accelerator treatment was measured using the same method as in Example 3, with the exception that thiomalic acid was used as accelerator solution suspension inhibiting compound, and the concentration was varied.
• the adsorption amount of palladium and tin on substrate after accelerator treatment was measured using the same method as in Example 4, with the exception that accelerator solution suspension inhibiting compound was not contained in the accelerator solution.
• the adsorption amount of palladium and tin on substrate after accelerator treatment was measured using the same method as in Example 4, with the exception that an accelerator solution was used that contained sulfuric acid at a concentration of 0.25 mol/L, which is a solution that is known to accelerate palladium tin catalyst.
• Example 4 The results of Example 4 and Comparative Examples 4 and 5 are shown in Table 4.
• Example 4 a retaining effect with respect to residual palladium and a reduction effect with respect to residual elemental tin amount were manifested starting at a thiomalic acid concentration of 0.002 g/L.
• the adsorption amount of palladium and tin on a substrate after accelerator treatment was measured using the same method as in Example 4, with the exception that the accelerator solution treatment time and the thiomalic acid concentration were varied, and the temperature of the accelerator solution was set at 40°C or 30°C.
• the adsorption amount of palladium and tin on substrate after accelerator treatment was measured using the same method as in Example 5, with the exception that accelerator solution suspension inhibiting compound was not contained.
• Example 5 The results for Example 5 and Comparative Example 6 are presented in Table 5.
• Example 5 As is clear from Example 5, a decrease in residual tin amount was seen at a treatment time of 3 min, regardless of whether the bath temperature was 30°C or 40°C, and in addition, the palladium retaining effect was improved relative to Comparative Example 6.
• a solution was prepared by using 0.05 g/L of thiomalic acid as the accelerator solution suspension inhibiting compound, and adding palladium tin catalyst solution to the accelerator solution.
• the added palladium tin catalyst solution was a solution containing palladium and tin at a weight ratio of 7:10,000, and the added amount was 0-10 mg/L in terms of tin concentration in the solution.
• the bath temperature was 30°C and the treatment time was 5.5 min. With these exceptions, the adsorption amount of palladium and tin on a substrate after accelerator treatment was measured using the same method as in Example 5.
• the adsorption amount of palladium and tin on a substrate after accelerator treatment was measured using the same method as in Example 6, with the exception that thiomalic acid was not contained.
• Example 6 The results for Example 6 and Comparative Example 7 are shown in Table 6.
• Example 6 tin and palladium were added to the accelerator solution. Actually, because the amount of tin and palladium in the bath increases when the use of accelerator solution was stopped, this test system is used as a model for accelerator solutions that are used for a determinate time period.
• the added amount of catalyst was changed in Comparative Example 7, and the amount of residual palladium present after treatment varied. On the other hand, even when the added amount of catalyst was changed in Example 6, there was almost no observed change in the residual amount of palladium.
• the solution is exchanged when the tin concentration in the solution reaches about 30 mg/L, although this will differ depending on parameters of use and other considerations. For this reason, it is desirable for the amount of adsorbed palladium not to vary when the tin concentration is in the range of 0-30 mg/L.
• the accelerator solution of the present invention has a constant adsorbed palladium amount over this range, and it is clear that changes in the palladium amount adhered to the substrate will be controlled, even when the tin content and palladium content vary during use in an industrial setting.
• the accelerator bath of the present invention contains accelerator solution suspension inhibiting compound, and as a result, it has the effect of inhibiting or reducing an increase in accelerator solution turbidity when use is interrupted, which has been a problem with conventional accelerator solutions.
• an effect is produced whereby it is possible to prevent roughening of deposited copper layers in copper-resin composite materials obtained by electrolytic copper plating treatments carried out after electroless copper plating. This is particularly true for electrolytic copper plating treatments that have low leveling capacity.
• the accelerator solution of the present invention has the effect of preventing a decrease in the adsorbed amount of palladium catalyst.

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• 2001
  • 2001-08-02 JP JP2001234424A patent/JP2003049279A/ja active Pending
• 2002
  • 2002-08-01 TW TW091117273A patent/TW548340B/zh not_active IP Right Cessation
  • 2002-08-01 EP EP02255393A patent/EP1281787A2/fr not_active Withdrawn
  • 2002-08-02 KR KR1020020045745A patent/KR20030013322A/ko not_active Withdrawn
  • 2002-08-02 CN CN02152914A patent/CN1408899A/zh active Pending

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